arXiv subjects

Emiliano Cortes

Publications and source records attributed to Emiliano Cortes.

14 recordsLinked to original sources

arXiv2026

Operando imaging of intercalation memory in MXenes

Ion intercalation enables reversible control of charge, structure and function in layered solids. Yet layered materials contain nanosheets with different thicknesses and stacking, whose intercalation pathways are averaged out in ensemble measurements. This becomes critical under Angstrom-scale confinement, where ion transport couples to solvent reorganization and host deformation, leaving the origins of kinetics, reversibility and activation unresolved. Here we combine operando interferometric scattering and interference reflection microscopy to resolve proton-driven dynamics in individual single- and multilayer Ti3C2Tx MXene flakes and show that even a few stacked layers introduce a significant kinetic barrier. Cycling then separates nanosheets into three persistent behaviors: reversible monolayers, restacked multilayers with incomplete recovery and delayed deintercalation, and coherently stacked multilayers that self-stabilize through reversible folding. Operando synchrotron X-ray diffraction shows this memory at electrode scale, where the interlayer structure converges towards a reproducible state. Our findings reveal cycling-induced structural memory that governs subsequent intercalation in layered MXenes.

physics.chem-ph↗

arXiv2025

Hot-carrier generation in bimetallic Janus nanoparticles

Energetic electrons and holes generated from the decay of localized surface plasmons in metallic nanoparticles can be harnessed in nanoscale devices for photocatalysis, photovoltaics or sensing. In this work, we study the generation of such hot carriers in bimetallic Janus nanoparticles composed of Au, Ag and Cu using a recently developed atomistic modelling approach that combines a solution of the macroscopic Maxwell equation with large-scale quantum-mechanical tight-binding models. We first analyze spherical Janus nanoparticles whose unique hot-carrier spectrum can be associated with the spectra of the two hemispheres and the interface coupling and find that under solar illumination the Ag-Au system exhibits the highest hot-carrier generation rate. For dumbbell-shaped Janus nanoparticles, we observe a significant increase in hot-carrier generation with increasing neck size. This is caused by a dramatic enhancement of the electric field in the neck region. We also study the dependence of hot-carrier generation on the light polarization and find that the largest generation rates are obtained when the electric field is perpendicular to the interface between the two metals due to the maximal dipole coupling with the electric field. The insights from our study will guide the experimental design of efficient hot-carrier devices based on bimetallic Janus nanoparticles.

physics.optics↗

arXiv2025

Optical and electrical probing of plasmonic metal-molecule interactions

Plasmonic nanostructures enable efficient light-to-energy conversion by concentrating optical energy into nanoscale volumes. A key mechanism in this process is chemical interface damping (CID), where surface plasmons are damped by adsorbed molecules, enabling the transfer of charge to adsorbed molecules. In this study, we investigate the relationship between CID and adsorbate-induced changes in DC electrical resistivity for four molecular adsorbates-adenine, 4-aminothiophenol (ATP), biphenyl thiol (BPT), and 1-dodecanethiol (DDT)-on gold surfaces. Our results reveal two distinct CID regimes. BPT causes CID via direct electronic transitions to the lowest unoccupied molecular orbital (LUMO), which is centered at approx. 2 eV above the Fermi level and can be resonantly excited by the plasmon. This mechanism is dependent on plasmon energy. In contrast, ATP, adenine and DDT lead to plasmon damping through inelastic electron scattering at the metal-molecule interface. This regime shows a weaker dependency on plasmon energy since it does not involve resonant electron excitation between hybridized metal-molecule states. This same mechanism contributes to adsorbate-induced changes in DC resistivity, suggesting that resistivity measurements can serve as a probe of plasmonic energy transfer, as highlighted by the good correlation between the two effects. These findings provide new insights into the microscopic origins of plasmon damping and offer a unified framework for understanding metal-adsorbate energy transfer.

physics.optics↗

arXiv2024

All-Optical Generation and Detection of Coherent Acoustic Vibrations in Single Gallium Phosphide Nanoantennas Probed Near the Anapole Excitation

Nanostructured high-index dielectrics have shown great promise as low-loss photonic platforms for wavefront control and enhancing optical nonlinearities. However, their potential as optomechanical resonators has remained unexplored. In this work, we investigate the generation and detection of coherent acoustic phonons in individual crystalline gallium phosphide nanodisks on silica in a pump-probe configuration. By pumping the dielectric above its bandgap energy and probing over its transparent region, we observe the radial breathing mode of the disk with an oscillation frequency around 10 GHz. We analyze the performance of nanoantennas of various sizes in the 300-600 nm diameter range at fixed 125 nm height and find that the detection efficiency is maximum near the fundamental anapole state, in agreement with numerical simulations. By comparing with reference gold nanodisk and nanorod plasmonic resonators, we find that the dielectric nanoantennas display a modulation amplitude up to ~5 times larger. We further demonstrate the launching of acoustic waves through the underlaying substrate and the mechanical coupling between two nanostructures placed 3 μm apart, laying the basis for photonic-phononic signal processing using dielectric nanoantennas.

physics.optics↗

arXiv2023

Semiconductor Metasurfaces for Surface-enhanced Raman Scattering

Semiconductor-based surface-enhanced Raman spectroscopy (SERS) substrates, as a new frontier in the field of SERS, are hindered by their poor electromagnetic field confinement, and weak light-matter interaction. Metasurfaces, a class of 2D artificial materials based on the electromagnetic design of nanophotonic resonators, enable strong electromagnetic field enhancement and optical absorption engineering for a wide range of semiconductor materials. However, the engineering of semiconductor substrates into metasurfaces for improving SERS activity remains underexplored. Here, we develop an improved SERS metasurface platform that leverages the combination of titanium oxide (TiO2) and the emerging physical concept of optical bound states in the continuum (BICs) to boost the Raman emission. Moreover, fine-tuning of BIC-assisted resonant absorption offers a pathway for maximizing the photoinduced charge transfer effect (PICT) in SERS. We achieve ultrahigh values of BIC-assisted electric field enhancement (|E/E0|^2 ~ 10^3), challenging the preconception of weak electromagnetic (EM) field enhancement on semiconductor SERS substrates. Our BIC-assisted TiO2 metasurface platform offers a new dimension in spectrally-tunable SERS with earth-abundant and bio-compatible semiconductor materials, beyond the traditional plasmonic ones.

physics.optics↗

arXiv2023

Theory of hot-carrier generation in bimetallic plasmonic catalysts

Bimetallic nanoreactors in which a plasmonic metal is used to funnel solar energy towards a catalytic metal have recently been studied experimentally, but a detailed theoretical understanding of these systems is lacking. Here, we present theoretical results of hot-carrier generation rates of different Au-Pd nanoarchitectures. In particular, we study spherical core-shell nanoparticles with a Au core and a Pd shell as well as antenna-reactor systems consisting of a large Au nanoparticle with acts as antenna and a smaller Pd satellite nanoparticle separated by a gap. In addition, we investigate an antenna-reactor system in which the satellite is a core-shell nanoparticle. Hot-carrier generation rates are obtained from an atomistic quantum-mechanical modelling technique which combines a solution of Maxwell's equation with a tight-binding description of the nanoparticle electronic structure. We find that antenna-reactor systems exhibit significantly higher hot-carrier generation rates in the catalytic material than the core-shell system as a result of strong electric field enhancements associated with the gap between the antenna and the satellite. For these systems, we also study the dependence of hot-carrier generation rate on the size of the gap, the radius of the antenna nanoparticle and the direction of light polarization. Our insights pave the way towards a mechanistic understanding of hot-carrier generation in heterogeneous nanostructures for photocatalysis and other energy conversion applications.

cond-mat.mtrl-sci↗

arXiv2023

Improved in-situ characterization of electrochemical interfaces using metasurface-driven surface-enhanced infrared absorption spectroscopy

Electrocatalysis plays a crucial role in realizing the transition towards green energy, driving research directions from hydrogen generation to carbon dioxide reduction. Understanding electrochemical reactions is crucial to improve their efficiency and to bridge the gap toward a sustainable zero-carbon future. Surface-enhanced infrared absorption spectroscopy (SEIRAS) is a suitable method for investigating these processes because it can monitor with chemical specificity the mechanisms of the reactions. However, it remains difficult to detect many relevant aspects of electrochemical reactions such as short-lived intermediates. Here, we develop and experimentally realize an integrated nanophotonic-electrochemical SEIRAS platform for the in situ investigation of molecular signal traces emerging during electrochemical experiments. Specifically, we implement a platinum nano-slot metasurface featuring strongly enhanced electromagnetic near fields and spectrally target it at the weak vibrational bending mode of adsorbed CO at ~2033 cm-1. Crucially, our platinum nano-slot metasurface provides high molecular sensitivity. The resonances can be tuned over a broad range in the mid-infrared spectrum. Compared to conventional unstructured platinum layers, our nanophotonic-electrochemical platform delivers a substantial improvement of the experimentally detected characteristic absorption signals by a factor of 27, enabling the detection of new species with weak signals, fast conversions, or low surface concentrations. By providing a deeper understanding of catalytic reactions, we anticipate our nanophotonic-electrochemical platform to open exciting perspectives for electrochemical SEIRAS, surface-enhanced Raman spectroscopy, and the study of reactions in other fields of chemistry such as photoelectrocatalysis.

cond-mat.mes-hall↗

arXiv2022

Advances in ultrafast plasmonics

In the past twenty years, we have reached a broad understanding of many light-driven phenomena in nanoscale systems. The temporal dynamics of the excited states are instead quite challenging to explore, and, at the same time, crucial to study for understanding the origin of fundamental physical and chemical processes. In this review we examine the current state and prospects of ultrafast phenomena driven by plasmons both from a fundamental and applied point of view. This research area is referred to as ultrafast plasmonics and represents an outstanding playground to tailor and control fast optical and electronic processes at the nanoscale, such as ultrafast optical switching, single photon emission and strong coupling interactions to tailor photochemical reactions. Here, we provide an overview of the field, and describe the methodologies to monitor and control nanoscale phenomena with plasmons at ultrafast timescales in terms of both modeling and experimental characterization. Various directions are showcased, among others recent advances in ultrafast plasmon-driven chemistry and multi-functional plasmonics, in which charge, spin, and lattice degrees of freedom are exploited to provide active control of the optical and electronic properties of nanoscale materials. As the focus shifts to the development of practical devices, such as all-optical transistors, we also emphasize new materials and applications in ultrafast plasmonics and highlight recent development in the relativistic realm. The latter is a promising research field with potential applications in fusion research or particle and light sources providing properties such as attosecond duration.

physics.optics↗

arXiv2021

Challenges on Optical Printing of Colloidal Nanoparticles

While colloidal chemistry provides ways to obtain a great variety of nanoparticles, with different shapes, sizes, material composition, and surface functions, their controlled deposition and combination on arbitrary positions of substrates remains a considerable challenge. Over the last ten years, optical printing arose as a versatile method to achieve this purpose for different kinds of nanoparticles. In this article we review the state of the art of optical printing of single nanoparticles, and discuss its strengths, limitations, and future perspectives, by focusing on four main challenges: printing accuracy, resolution, selectivity, and nanoparticles photostability.

cond-mat.mes-hall↗

arXiv2021

In Situ Photothermal Response of Single Gold Nanoparticles Through Hyperspectral Imaging AntiStokes Thermometry

Several fields of applications require a reliable characterization of the photothermal response and heat dissipation of nanoscopic systems, which remains a challenging task both for modeling and experimental measurements. Here, we present a new implementation of anti-Stokes thermometry that enables the in situ photothermal characterization of individual nanoparticles (NPs) from a single hyperspectral photoluminescence confocal image. The method is label-free, applicable to any NP with detectable anti-Stokes emission, and does not require any prior information about the NP itself or the surrounding media. With it, we first studied the photothermal response of spherical gold NPs of different sizes on glass substrates, immersed in water, and found that heat dissipation is mainly dominated by the water for NPs larger than 50 nm. Then, the role of the substrate was studied by comparing the photothermal response of 80 nm gold NPs on glass with sapphire and graphene, two materials with high thermal conductivity. For a given irradiance level, the NPs reach temperatures 18% lower on sapphire and 24% higher on graphene than on bare glass. The fact that the presence of a highly conductive material such as graphene leads to a poorer thermal dissipation demonstrates that interfacial thermal resistances play a very significant role in nanoscopic systems, and emphasize the need for in situ experimental thermometry techniques. The developed method will allow addressing several open questions about the role of temperature in plasmon-assisted applications, especially ones where NPs of arbitrary shapes are present in complex matrixes and environments.

physics.optics↗

arXiv2020

Electrical control of single-photon emission in highly-charged individual colloidal quantum dots

Electron transfer to an individual quantum dot promotes the formation of charged excitons with enhanced recombination pathways and reduced lifetimes. Excitons with only one or two extra charges have been observed and exploited for very efficient lasing or single quantum dot LEDs. Here, by room-temperature time-resolved experiments on individual giant-shell CdSe/CdS quantum dots, we show the electrochemical formation of highly charged excitons containing more than twelve electrons and one hole. We report the control over intensity blinking, along with a deterministic manipulation of quantum dot photodynamics, with an observed 210-fold increase of the decay rate, accompanied by 12-fold decrease of the emission intensity, while preserving single-photon emission characteristics. These results pave the way for deterministic control over the charge state, and room-temperature decay-rate engineering for colloidal quantum dot-based classical and quantum communication technologies.

physics.optics↗

arXiv2020

Size-Selective Optical Printing of Silicon Nanoparticles through Their Dipolar Magnetic Resonance

Silicon nanoparticles possess unique size-dependent optical properties due to their strong electric and magnetic resonances in the visible range. However, their widespread application has been limited, in comparison to other (e.g. metallic) nanoparticles, because their preparation on monodisperse colloids remains challenging. Exploiting the unique properties of Si nanoparticles in nano- and micro-devices calls for methods able to sort and organize them from a colloidal suspension onto specific positions of solid substrates with nanometric precision. Here, we demonstrate that surfactant-free Silicon nanoparticles of a predefined and narrow ($σ$ < 10 nm) size range can be selectively immobilized on a substrate by optical printing from a polydisperse colloidal suspension. The size selectivity is based on differential optical forces that can be applied on nanoparticles of different sizes by tuning the light wavelength to the size-dependent magnetic dipolar resonance of the nanoparticles.

physics.optics↗

arXiv2017

Decoupling absorption and emission processes in super-resolution localization of emitters in a plasmonic hotspot

The absorption process of an emitter close to a plasmonic antenna is enhanced due to strong local electromagnetic (EM) fields. The emission process, if resonant with the plasmonic system, re-radiates to the far-field by coupling with the antenna due to the availability of plasmonic states. This increases the local density of states (LDOS), effectively providing more, or alternate, pathways for emission. Through the mapping of localized emission events from single molecules close to plasmonic antennas, performed using far-field data, one gains combined information on both the local EM field strength and the LDOS available. The localization from these emission-coupled events generally do not, therefore, report the real position of the molecules, nor the EM enhancement distribution at the illuminating wavelength. Here we propose the use of a large Stokes shift fluorescent molecule in order to spectrally decouple the emission process of the dye from the plasmonic system, leaving only the absorption strongly in resonance with the enhanced EM field in the antennas vicinity. We show that the real position of the emitters in this complex, but interesting, scenario can be found directly. Moreover, we demonstrate that this technique provides an effective way of exploring either the EM field or the LDOS with nanometre spatial resolution.

physics.optics↗

arXiv2016

Plasmonic nanoprobes for stimulated emission depletion microscopy

Plasmonic nanoparticles influence the absorption and emission processes of nearby emitters due to local enhancements of the illuminating radiation and the photonic density of states. Here, we use the plasmon resonance of metal nanoparticles in order to enhance the stimulated depletion of excited molecules for super-resolved microscopy. We demonstrate stimulated emission depletion (STED) microscopy with gold nanorods with a long axis of only 26 nm and a width of 8 nm that provide an enhancement of the resolution compared to fluorescent-only probes without plasmonic components irradiated with the same depletion power. These novel nanoparticle-assisted STED probes represent a ~2x10^3 reduction in probe volume compared to previously used nanoparticles and we demonstrate their application to the first plasmon-assisted STED cellular imaging. We also discuss their current limitations.

physics.optics↗